Derivatives of decahydro-cycloprop[e]indene compounds and their use in perfume compositions

ABSTRACT

The present invention is directed to novel substituted cyclopropane ethers compounds of the general formulae selected from the group consisting of  
                 
wherein R represent a hydrogen or a straight, branched, or cyclic hydrocarbon moiety consisting of less then 15 carbon atoms and containing single and/or double bonds and R1 represents a methyl or ethyl group.

STATUS OF RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 11/286,189,filed on Nov. 23, 2005, now allowed, the contents herby incorporated byreference as if set forth in its entirety.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how differences in the chemical structure ofthe molecule can result in significant differences in the odor, notesand characteristics of a molecule. These variations and the ongoing needto discover and use the new chemicals in the development of newfragrances allows perfumers to apply the new compounds in creating newfragrances.

SUMMARY OF THE INVENTION

The present invention provides novel chemicals, and the use of thechemicals to enhance the fragrance of perfumes, toilet waters, colognes,personal products and the like. In addition, the present invention isdirected to the use of the novel chemicals to enhance fragrance inperfumes, toilet waters, colognes, personal products and the like.

More specifically, the present invention is directed to the noveldecahydro-cycloprop[e]indene compounds, represented by the generalstructures of Formulae I-III set forth below:

-   -   wherein R represent a hydrogen or a straight, branched, or        cyclic hydrocarbon moiety consisting of less then 15 carbon        atoms and containing single and/or double bonds and R1        represents a methyl or ethyl group.

Another embodiment of the invention is a method for enhancing a perfumecomposition by incorporating an olfactory acceptable amount of thecompounds provided above.

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

In Formulae I, II and III above, R independently represent a hydrogen ora straight, branched, or cyclic hydrocarbon moiety consisting of lessthen 15, preferably less then 10, most preferably less then 7 carbonatoms and containing single and/or double bonds and R1 represents amethyl or ethyl group.

Suitable straight hydrocarbon moieties include ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. Suitablebranched hydrocarbon moieties include isopropyl, sec-butyl, tert-butyl,2-ethyl-propyl, and the like. Suitable cyclic hydrocarbon moietiesinclude cyclopropane, cyclobutane, cyclopentane, cyclopentene,1,4-cyclopentene, cyclohexane, cyclohexene and the like. Suitablehydrocarbon moieties containing double bonds include ethene, propene,1-butene, 2-butene, penta-1-3-deine, hepta-1,3,5-triene and the like.

In the preferred embodiment of the invention, the novel compounds of thepresent invention are represented by the following structures:

Those with the skill in the art will appreciate that the compound ofFormula IV is6b-methoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene; thecompound of Formula V is6b-ethoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene; thecompound of Formula VI is1a-methoxy-5,5,6,7,7-pentamethyl-octahydro-cyclopropa[d]indene; thecompound of Formula VII is1a-ethoxy-5,5,6,7,7-pentamethyl-octahydro-cyclopropa[d]indene; thecompound of Formula VIII is 1-methoxy-2-octyl-cyclopropane and thecompound of Formula IX is 1-ethoxy-2-octyl-cyclopropane.

The table below lists additional compounds derived from Formula I thatare described in the present invention: R Compound (CH₂)₂CH₃6b-propoxy-4,4,5,6,6,-pentamethyl-decahydro- cyclopropa[e]indene(CH₂)₄CH₃ 6b-pentyloxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene CHCH(CH₂)₃CH₃6b-hex-1-enyloxy-4,4,5,6,6,-pentamethyl-decahydro- cyclopropa[e]indeneCH(CH₃)₂ 6b-isopropoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene C(CH₃)₃6b-tert-butoxy-4,4,5,6,6,-pentamethyl-decahydro- cyclopropa[e]indeneCHCH₂ 6b-vinyloxy-4,4,5,6,6,-pentamethyl-decahydro- cyclopropa[e]indene

6b-cyclopentyloxy-4,4,5,6,6,-pentamethyl-decahydro- cyclopropa[e]indene

6b-cyclohexyloxy-4,4,5,6,6,-pentamethyl-decahydro- cyclopropa[e]indene

6b-(cyclohex-2-enyloxy)-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene

6b-cyclopentyloxy-4,4,5,6,6,-pentamethyl-decahydro- cyclopropa[e]indene

The table below lists additional compounds derived from Formula II thatare described in the present invention: R R1 Compound CH₃CHCH₂CH₃ CH₃1-sec-butyl-2-methoxy-cyclopropane CHC(CH₃)₃ CH₃1-(2,2-dimethyl-propyl)-2-methoxy-cyclopropane CH₃(CH)₂(CH₂)₄CH₃ CH₃1-methoxy-2-oct-2-enyl-cyclopropane (CH₂)₆CH CH₃1-methoxy-2-oct-7-ynyl-cyclopropane (CH₂)₇CH₃ CH₂CH₃1-ethoxy-2-octyl-cyclopropane (CH₂)₂CH₃ (CH₂)₂CH₃1-propoxy-2-propyl-cyclopropane (CH₂)₇CH₃ (CH₂)₇CH₃1-octyl-2-octyloxy-cyclopropane

CH₃ [2-(2-methoxy-cyclopropyl)-ethyl]-cyclopentane

(CH₂)₃CH₃ [2-(2-butoxy-cyclopropyl)-ethyl]-cyclopentane

CH₃ (2-methoxy-cyclopropylmethyl)-cyclohexane

CH₂CH₃ (2-ethoxy-cyclopropylmethyl)-cyclohexane

The compounds of the present invention may be prepared from thecorresponding compounds containing a double bond by Simmon-Smithreaction of the following sequences:

The alkenes used in the above reaction to prepare the compounds of thepresent invention are disclosed in U.S. Pat. Nos. 5,665,698 and5,733,866. Two of the possible precursors of the compounds of thepresent invention are 1-methoxy-1-decene and 1-ethoxy-1-decene.

Those with skill in the art will recognize that some of the compounds ofthe present invention have a number of chiral centers, thereby providingnumerous isomers of the claimed compounds. It is intended herein thatthe compounds described herein include isomeric mixtures of suchcompounds, as well as those isomers that may be separated usingtechniques known to those having skill in the art. Suitable techniquesinclude chromatography such as High Performance Liquid Chromatography(“HPLC”), and particularly gel chromatography and solid phasemicroextraction (“SPME”).

We have discovered that the compounds of Formulae IV-VII have warm,woody, cashmeran, ambery, nitro musk notes and compounds of FormulaeVIII and IX display an aldehydic, fresh citrus note that are well suitedfor use as a fragrance ingredient.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products as well as air fresheners and cosmeticpreparations. The present invention can also be used to perfume cleaningagents, such as, but not limited to detergents, dishwashing materials,scrubbing compositions, window cleaners and the like.

In these preparations, the compounds of the present invention can beused alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility with the other components beingemployed. Suitable fragrances include but are not limited to fruits suchas almond, apple, cherry, grape, pear, pineapple, orange, strawberry,raspberry; musk, flower scents such as lavender-like, rose-like,iris-like, carnation-like. Other pleasant scents include herbal andwoodland scents derived from pine, spruce and other forest smells.Fragrances may also be derived from various oils, such as essentialoils, or from plant materials such as peppermint, spearmint and thelike.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

Olfactory effective amount is understood to mean the amount of compoundin perfume compositions the individual component will contribute to itsparticular olfactory characteristics, but the olfactory effect of theperfume composition will be the sum of the effects of each of theperfumes or fragrance ingredients. Thus the compounds of the inventioncan be used to alter the aroma characteristics of the perfumecomposition, or by modifying the olfactory reaction contributed byanother ingredient in the composition. The amount will vary depending onmany factors including other ingredients, their relative amounts and theeffect that is desired.

The level of compound of the invention employed in the perfumed articlevaries from about 0.005 to about 10 weight percent, preferably fromabout 0.5 to about 8 and most preferably from about 1 to about 7 weightpercent. In addition to the compounds other agents can be used inconjunction with the fragrance. Well known materials such assurfactants, emulsifiers, polymers to encapsulate the fragrance can alsobe employed without departing from the scope of the present invention.

Another method of reporting the level of the compounds of the inventionin the perfumed composition, i.e., the compounds as a weight percentageof the materials added to impart the desired fragrance. The compounds ofthe invention can range widely from 0.005 to about 70 weight percent ofthe perfumed composition, preferably from about 0.1 to about 50 and mostpreferably from about 0.2 to about 25 weight percent. Those with skillin the art will be able to employ the desired level of the compounds ofthe invention to provide the desired fragrance and intensity.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. As used herein all percentagesare weight percent unless otherwise noted, ppm is understood to standfor parts per million and g is understood to be grams. All U.S. patentsmentioned above are incorporated herein by reference. IFF as used in theexamples is understood to mean International Flavors & Fragrances Inc.,New York, N.Y., USA. All fragrance materials mentioned in the examplesare available from IFF.

EXAMPLE A Preparation of6b-methoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene

To a dry 500 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 8 g of ZnCu, 70ml of Methyl Tertiary Butyl Ether (MTBE) and 3 crystals of I₂ were addedand stirred. 23 g of CH₂I₂ was added while stirring. A heating sourcewas applied to the mixture. 22 g of7-methoxy-1,1,2,3,3-pentamethyl-2,3,3a,4,5,7a-hexahydro-1H-indne wasadded drop-wise over 20 minutes. The mixture was aged for 7.5 hours. Themixture was quenched with saturated NH₄Cl, aqueous layer separated andthe organic layer washed with 200 ml of water. The organic layer wasthen dried over anhydrous MgSO₄.

The NMR of the6b-methoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene is asfollows: 0.6 ppm (m, 4H); 0.7 ppm (m, 1H); 0.8 ppm (s, 3H); 0.9 ppm (s,4H); 1.0 ppm (s, 2H); 1.1 ppm (s, 7H); 1.2 ppm (m, 2H); 1.2 ppm (m, 1H);1.3 ppm (m, 1H); 2.1 ppm (d, 1H); 2.2 ppm (m, 1H); 3.3 ppm (s, 3H).

EXAMPLE B Preparation of6b-ethoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene

To a dry 200 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 1 g of ZnCu, 30ml of Methyl Tertiary Butyl Ether (MTBE) and 1 crystal of I₂ were addedand stirred. 3.3 g of CH₂I₂ was via syringe. The mixture was heatedmaintained at 60° C. 1.97 g of7-ethoxy-1,1,2,3,3-pentamethyl-2,3,3a,4,5,7a-hexahydro-1H-indne wasadded in one portion. The mixture was aged for 7.5 hours. The mixturewas quenched with saturated NH₄Cl, aqueous layer separated and theorganic layer washed with 200 ml of water. The organic layer was thendried over anhydrous MgSO₄.

The NMR of the6b-ethoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene is asfollows: 0.2 ppm (s, 1H); 0.8 ppm (m, 10H); 1.0 ppm (d, 8H); 1.2 ppm (m,3H); 1.3 ppm (m, 1H); 1.5 ppm (m, 2H); 1.6 ppm (s, 2H); 1.6-1.7 ppm (m,1H); 1.8 ppm (d, 1H); 2.3 ppm (d, 1H); 3.3 ppm (m, 1H); 3.7 ppm (m, 1H).

EXAMPLE C Preparation of 1-methoxy-2-octyl-cyclolprolpane

To a dry 200 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 100 ml ofdiethyl Ether, 7.5 g of ZnCu and 27 g of g of CH₂I₂ were added, stirredand heated to reflux. 3.3 was via syringe. The mixture was heatedmaintained at 60° C. In 30 minutes 170 g 1-methoxy-1-decene was addeddropwise via the addition funnel. A crystal of I₂ was added and themixture was aged overnight. The mixture was quenched with saturatedNH₄Cl, aqueous layer separated and the organic layer washed with 200 mlof water. The organic layer was then dried over anhydrous MgSO₄.

The NMR of the 1-methoxy-2-octyl-cyclopropane is as follows: 0.1 ppm (s,1H); 0.2 ppm (m, 1H); 0.6 ppm (m, 1H); 0.7 ppm (m, 1H); 0.8 ppm (m, 1H);0.9 ppm (s, 3H); 1.1 ppm (m, 1H); 1.3 ppm (s, 8H); 1.4 ppm (m, 2H); 2.9ppm (s, 1H); 3.2 ppm (s, 1H); 3.3 ppm (s, 1H); 3.4 ppm (s, 1H).

EXAMPLE D Preparation of 1-ethoxy-2-octyl-cyclolprolpane

To a dry 200 ml multi-neck round bottom flask fitted with an airstirrer, nitrogen inlet condenser and an addition funnel 10 ml ofdiethyl Ether, 2 g of ZnCu and 1 crystal of I₂ were added and stirredfor 5 minutes. 3.3 g of g of CH₂I₂ were added to the mixture and themixture was heated to 60° C. In 30 minutes 2 g 1-ethoxy-1-decene wasadded in one portion. The mixture was aged overnight. The mixture wasquenched with saturated NH₄Cl, aqueous layer separated and the organiclayer washed with 2 100 ml portions of water. The organic layer was thendried over anhydrous MgSO₄.

The NMR of the 1-ethoxy-2-octyl-cyclopropane is as follows: 0.1 ppm (s,1H); 0.2 ppm (m, 1H); 0.6 ppm (m, 1H); 0.7 ppm (s, 1H); 0.8 ppm (s, 1H);0.9 ppm (s, 3H); 1.1 ppm (m, 4H); 1.3 ppm (s, 11H); 1.4 ppm (m, 2H); 2.9ppm (s, 1H); 3.2 ppm (s, 1H); 3.6 ppm (s, 2H).

EXAMPLE E Incorporation of6b-methoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene into aFragrance Formulation

A fragrance was prepared according to the following formulation:4h-Pyran-4-One, 2-Ethyl-3-Hydroxy 10% 3.00 Aldehyde AA Triplal 3.00Anisaldehyde para 25.00 Benzyl Acetate 20.00 Benzyl Salicylate 35.00Cyclamal 30.00 6b-methoxy-4,4,5,6,6,-pentamethyl- 25.00decahydro-cyclopropa[e]indene Dihydro Methyl Jasmonate 100.00 EthylVanillin 10% 4.00 Galaxolide 175.00 Geraniol 100.00 Helional 45.00Hexenyl Acetate, Cis-3 3.00 Hexenyl Salicylate, Cis-3 40.00 HexylSalicylate 15.00 Hydrocinnamaldehyde, Para Tertiary Butyl Alpha Methyl90.00 Hydroxycitronellal 35.00 Nerol 70.00 Phenyl Ethyl Alcohol 150.00Piperonal 15.00 Terpineol 15.00 Undecalactone Gamma 2.00 Total weight1000.00

This fragrance was described as having warm, woody, cashmeran, amberyodor notes.

EXAMLE F Incorporation of6b-ethoxy-4,4,5,6,6,-pentamethyl-decahydro-cyclopropa[e]indene into aFragrance Formulation

A fragrance was prepared according to the following formulation:2-Adamantanol, 4-Methyl-8-Methylene 200.00 Aldehyde AA Triplal 3.00Cardamom Oil Ceylon LMR 5.00 6b-ethoxy-4,4,5,6,6,-pentamethyl- 17.00decahydro-cyclopropa[e]inden Dihydro Methyl Jasmonate 115.00 Galaxolide75.00 Iso E Super 225.00 Koavone 175.00 Linalool 35.00 Linalyl Acetate35.00 Lyral 25.00 Methyl Ionone Gamma 45.00 Pepper Oil Black 5.00 ThymeOil White LMR 3.00 Tobacco Leaf Absolute 2.00 Tonalid 35.00 Total weight1000.00

This fragrance was described as having warm, woody, cashmeran, amberyodor notes.

EXAMPLE G Incorporation of 1-methoxy-2-octyl-cyclopropane into aFragrance Formulation

A fragrance was prepared according to the following formulation:Acetaldehyde DEA 10% DPG 15 1-methoxy-2-octyl-cyclopropane 12 Calone 10Cyclamal Extra 22 Eth Buty “F&F” 6.6 Eth Meth Phen Glyc 10 Eth-2-MethButy 5 Hexenol, beta, gamma, Cis 10% DPG 170 Hexenyl Iso Buty, cis-3 10%DPG 8.5 Iso Amy Acet 10 Iso Amyl Buty 45 Lemon Terpenes Dist ”PFG” 50Lilal 52 Linalyl Acet 0.8 Linalyl Iso Buty “F&F” 14 Melonal Giv 10% DPG60 Nona Dienol, 2-trans-6 US 1% DEP 10 Oxyphenylon 3 Phenyl Eth AlcWhite Extra 2 Pineapple Comp 1% DPG 3.8 Prenyl Acetate 0.5 Scentenal 10%DPG 3 Terpineol, Alpha 0.8 Undecalactone, Gamma 10 Vanillin 3 DIPG 273Total weight 800

This fragrance was described as having aldehydic and fresh citrus odornotes.

EXAMPLE G Incorporation of 1-ethoxy-2-octyl-cyclopropane into aFragrance Formulation

A fragrance was prepared according to the following formulation:Acetaldehyde DEA 10% DPG 15 Cyclopropanated 1-ethoxy-1-decene 12 Calone10 Cyclamal Extra 22 Eth Buty “F&F” 6.6 Eth Meth Phen Glyc 10 Eth-2-MethButy 5 Hexenol, beta, gamma, Cis 10% DPG 170 Hexenyl Iso Buty, cis-3 10%DPG 8.5 Iso Amy Acet 10 Iso Amyl Buty 45 Lemon Terpenes Dist ”PFG” 50Lilal 52 Linalyl Acet 0.8 Linalyl Iso Buty “F&F” 14 Melonal Giv 10% DPG60 Nona Dienol, 2-trans-6 US 1% DEP 10 Oxyphenylon 3 Phenyl Eth AlcWhite Extra 2 Pineapple Comp 1% DPG 3.8 Prenyl Acetate 0.5 Scentenal 10%DPG 3 Terpineol, Alpha 0.8 Undecalactone, Gamma 10 Vanillin 3 DIPG 273Total weight 800.00

This fragrance was described as having aldehydic and fresh citrus odornotes.

1. A compound of formula

wherein R represent a hydrogen or a straight, branched, or cyclichydrocarbon moiety consisting of less then 15 carbon atoms andcontaining single and/or double bonds and R1 represents a methyl orethyl group.
 2. A compound of claim 1, wherein R is a straighthydrocarbon moiety consisting of less then 10 carbon atoms.
 3. A methodof improving, enhancing or modifying a fragrance formulation through theaddition of an olfactory acceptable amount of the compound of claim 2.4. The method of claim 3 wherein the fragrance is incorporated into aproduct selected from perfumes, colognes, toilet waters, cosmeticproducts, personal care products, fabric care products, cleaningproducts and air fresheners.
 5. The method of claim 4 wherein thecleaning product is selected from the group consisting of detergents,dishwashing compositions, scrubbing compounds and window cleaners. 6.The method of claim 5, wherein the amount incorporated into a fragranceis from about 0.005 to about 10 weight percent.
 7. The method of claim6, wherein the amount incorporated into a fragrance is from about 0.5 toabout 8 weight percent.
 8. The method of claim 6, wherein the amount ofincorporated into a fragrance is from about 1 to about 7 weight percent.9. A fragrance formulation containing an olfactory effective amount ofthe compound of claim
 1. 10. A fragrance product containing a compoundof claim 1.